CA1240680A - Substituted 4,5-dimethoxypyridazones, herbicides containing these compounds, and their use for controlling undesirable plant growth - Google Patents

Abstract

Abstract of the Disclosure: 4,5-Dimethoxypyridazones of the formula

Description

~ lZ4~680 - 1 - O.Z. 0050t36555 ., The present invent;on relates to substituted 4,5-dimethoxypyridazones, herbicides ~h;ch contaln these pyr;dazones as act;ve ;ngred;ents, and methods of con-trolllng undes;rable plant growth w;th these act;ve ;ngred;ents or herb;cides.
It is known that 1-phenyL-4,5-d;methoxypyr;daz-6-one has a broad herb;c;dal act;on and can be used as a total herb;c;de tU.S. Patent 3,326,660). The act;ve ;ngred;ent can cause damage to plants both ~hen appl;ed before plant;ng the plant~ and when the leaves are treated. 4~5-Disubst;tuted 1-~m-tr;fluoromethylphenyl)-pyr;daz-6-ones and 4,5-d;subst;tuted 1-phenoxyphenylpyr;-daz-6-ones having similar herbicidal propert;es are also known ~U.S. Patents 3,697,522 and 4,360,672).
It has now been found that substituted 4,5-dimethoxypyridazones of the formula 3 (1) N
~ Y -(CR1R2) -Y -(CRlR2) - ~ z23 ~here X and Y ;ndependently of one another are each oxy-gen, sulfur, a sulf;nyl group or a sulfo group, R1 and R2 ;ndependently-of one another are each hydrogen or C1-C4-alkyl, z1, z2 and Z3 ;ndependently of one another are each hydrogen, halogen, n;tro, cyano, C1-C4-aLkyl, c1-c4-ha~oa~kyl! C1-C4-alkXY~ C1-C4 halalkoxy~
C1-C4-alkylmercapto, C1-C4-haloalkylmercapto, C1-C4-alkylsulf;nyl or C1-C4-alkylsulfonyl, n and p are each 0 or 1 and m and q are each 0 to 8,.with the proviso that m and q are not simultaneously equal to 0, possess good herbicidal J~R
,~ ~

lZ4~6~30

- 2 - O.Z. 0050/36555 activity and surpris;ngly are tolerated by crops or have a selective herb;cidal action when used in crops.
In formula I, R1 and R2 independently of one another can each be hydrogen or C1-C4-alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl or tert.-butyl, and z1, z2 and Z3 independently of one another can each be, for example, hydrogen, halogen, such as fluorine, chlor;ne or brom;ne, n;tro, cyano, C1-C4-alkyl, such as methyl, ethyl, n-propyl, ;-propyl, n-butyl or tert.-butyl, C1-C4-haloalkyl, such as trifluoromethyl, difluoromethyl, fluoro-methyl, trichloromethyl, dichloromethyl, chloromethyl, di-fluorochloromethyl, 1-chloroethyl, 2-chloroethyl, 1-fluoro-ethyl, 2-fluoroethyl, 2,2,2-tr;chloroethyl, 2,2,Z-tr;-fluoroethyl, 1,1,Z,2-tetrafluoroethy~, 1,1~Z-tri f luoro-2-chloroethyl or 1,1,2,2,2-pentafluoroethyl, C1-C4-alkoxy, such as methoxy, ethoxy, n-propoxy, ;-propoxy or tert.-bu-toxy, C1-C4-haloalkoxy, such as tr;chloromethoxy, tri-fluoromethoxy, 1-chloroethoxy, 2-chloroethoxy, 1-fluoro-ethoxy, 2-fluoroethoxy, 2,Z,2-trichloroethoxy, 2,2,2-tri-fluoroethoxy, 1,1,2,2-tetrafluoroethoxy or 1,1,2,2,2-penta-fluoroethoxy, C1-C4-alkylmercapto, such as methylmercapto or ethylmercapto, C1-C4-haloalkylmercapto, such as tri-chloromethylmercapto or trifluoromethylmercapto, C1-C4-alkylsulfinyl, such as methylsulfinyl or ethylsulfinyl, or C1-c4-alkylsulfonyl~ such as methylsulfonyl or ethyl-sulfonyl.
Preferred compounds of the formula I are those in which X and Y independently of one another are each oxygen or sulfur, R1 and R2 independently of one another are each hydrogen or C1-C4-alkyl, z1, z2 and Z3 independently of one another are each hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, n and p are each O or 1 and m and q are each O to 8.
Other preferred compounds of the formula I are those in which R1 and R2 are each hydrogen, z1 ;5 hydrogen, z2 and Z3 are each halogen, n is 0, m and p are each 1 and q is 0.

-- lZ4J~i80

- 3 - O.Z. 0050/36555 ~ The 4,5-dimethoxypyridazones of the formuLa I are obtained by reacting a 4,5-d;halopyr;dazone of the formula .al ~al (IV), X~Cfi ~ )~Yp(C )q ~ 2 where X, Y, R1, R2, z1, z2, z3, n, m, p and q have the above mean;ngs and Hal is halogen, ;n particular chlorine or bromine, with about the stoichiometr;c amount of an alkali metal methylate ;n the presence of an inert organic solvent at in general no higher than 100C, under atmos-pheric or superatmospheric pressure (from 1 to 10 bar), continuously or batchwise tprocess a)O
~ If 1-~3'-(4"-chlorobenzyloxy)-phenyl]-4,5-dichloro-pyridaz-6-one and sodium methylate are used as starting materials, the course of the reaction can be represented by the following equation:

~Cl -2 NaCl ~OCH~

151 ~ 2 NaOCEl > ,~
~CH--~Cl ~JLOCEI2-~C1 (IV) (I) Advantageously, the dihalopyridazone IV is first dissolved or suspended in an organic solvent, eg. toluene, and then reacted with the appropriate amount of the alco-holate. The reaction takes place under atmospheric or superatmospheric pressure, in general in the course of 12 hours at no higher than 100C, preferably from 40 to 80C, and can be carried out batchwise or continuously. The reaction mixture can be worked up in a conventional manner.

~Z4~68~

- 4 - O.Z. 0050/36555 If the end product ;s obta;ned ;n solid form, ;t ;s iso-lated by, for example, filter;ng off the prec;pitate under suct;on. If, on the other hand, the end product rema;ns d;ssolved ;n the solvent, the latter ;s d;st;lled off under reduced pressure, the res;due ;s st;rred w;th water, and the product is f;ltered off under suction. The pro-duct can be purif;ed by, for example, recrystall;zation or chromatography.
Dihalopyridazones of the formula IV can be obta;ned, for example, by react;ng a phenylhydrazine of the formula V

~Xn(CR1R2)mYp (CRlE~2)~-~Z (V~

where X, Y, R1, R2, z1, z2, z3, n, m, p and q have the above mean;ngs, w;th a 3-formyl-2,3-d;haloacryl;c ac;d of the formula ~o2c-c-- c cao ~al ~ (VI) where Hal ;s chlor;ne or brom;ne, and subject;ng the result;ng d;haloacrylic ac;d sem;carbazone to a cycliza-tion react;on.
The convers;on to the corresponding dihaloacrylicacid sem;carbazone ;s carried out at room temperature, for examp~e ;n an aqueous solut;on contain;ng a m;neral acid or ;n a water-conta;n;ng or anhydrous organ;c solvent, such as ethanol, wh;ch is evaporated off when the reaction ;s complete. Th;s sem;carbazone, preferably without be;ng isolated beforehand, ;s then cycl;zed to g;ve the d;halo-pyr;dazone of the formula IV by bo;l;ng ;n glac;al acet;c ac;d or acet;c anhydr;de or by heating ;n an aqueous m;ne-ral ac;d, eg. hydrochlor;c ac;d, at no h;gher than 100Cor by st;rr;ng ;n 3 concentrated m;neral ac;d, eg.

- lZ~6~3V

- 5 - O.Z. 0050/36555 sulfuric acid, at room temperature (German La;d-Open Applications DOS 1,695,840, DOS 2,526,643 and D9S
1,545,595). The reaction can be carried out batchwise or continuously, and the product can be worked up by a con-vent;onal method.
The 4,5-d;methoxypyr;dazones of the fornula I
where X ;s oxygen or sulfur and n ;s 1 can be prepared by react;ng a 4,5-d;methoxypyr;dazone of the formula pc~3 N`N~O (II) ~ .
where X is oxygen or sulfur, with about the sto;ch;ometric amount of an alkyl halide of the formula Hal- ( CR 1 R2 ) -Yp - ( CR R )q - ~ z23 (III) where R1 R2 y z1, z2, z3, m, p and q have the above mean;ngs and Hal is halogen, in particular chlor;ne or brom;ne, ;n the presence of an ;nert organic solvent and ;n the presence or absence of an ac;d acceptor at from O
to 150C. The react;on can be carried out under atmos-pher;c or superatmospher;c pressure, cont;nuously or batch-w;se (process b~.
If 1-t3'-hydroxyphenyl)-4,5-dimethoxypyr;daz-6-one and benzyl chlor;de are used as starting materials, the course of the reaction can be represented by the fol-lowing equation:

- ~24S~'681)

- 6 - O.Z. 0050/36555 oc~.3 OCY.3 ~CH3 ClC~.2~

The starting materials are used in about stoich;o-metric amounts, ie. ;n an amount of from 0.9 to 1.1 moles of start;ng mater;al III per mole of II. If necessary, an ac;d acceptor can be added ;n order to complete the reac-tion. Furthermore, the hydrogen hal;de formed during thereact;on can be expeLled by pass;ng in an ;nert gas, such as n;trogen. The process ;s advantageousLy carried out as follows: a solution of the ben7yl chloride III in an inert organ;c solvent is run, at 0 - 309C, if appropriate simultaneously with an equimolar amount of an ac;d accep-tor, into a solution or suspens;on of the start;ng mate-r;al II in an ;nert organic solvent, eg. dimethylformam;de.
To complete the reaction, st;rr;ng is continued for from 0.5 to 48, preferably from 2 to 12, hours at from 15 30 to 150C. The reaction mixture is ~orked up in a con- i ventional manner. If the end product is obta;ned in solid form, it is isolated by, for example, filtering off the precip;tate under suction. If, on the other hand, the end product rena;ns d;ssolved ;n the solvent, the latter ;s distilled off under reduced pressure, the residue is stirred with water, and the product is then filtered off under suction. The product can be purified by, for example, recrystallizat;on or chromatography.
Solvents which can be used for the two procPsses a) and b~ are organic solvents wh;ch are inert under the particular reaction conditions. Examples of suitable sol-vents are halohydrocarbons, in particular chlorohydrocar-bons, eg. tetrachloroethylene, 1,1,2,2- and 1,1,1,2-tetra-chloroethane, dichloropropane, methylene chloride, lZ4~68~)

- 7 - O.Z. 0050t36555 d;chlorobutane, chloroform, chloronaphthalene, d;chloro-naphthalene, carbon tetrachlor;de, 1,1,1- and 1,1,2-tr;-chloroethane, tr;chloroethylene, pentachloroethane, o-, m-and p-d;fluorobenzene, 1,2-dichloroethane, 1,1-dichloro-ethane, 1,2-c;s-d;chloroethylene, chlorobenzene, fluoro-benzene, bromobenzene, ;odoben7ene, o-, p- and m-dichloro-benzene, o-, p- and m-d;bromobenzene, o-, m- and p-chloro-toluene and 1,2,4-tr;chlorobenzene; ethers, eg. ethyl propyl ether, methyl tert.-butyl ether, n-butyl ethyl ether, di-n-butyl ether, d;;sobutyl ether, d;;soamyl ether, d;;sopropyL ether, an;sole, phenetole, cyclohexyl methyl ether, d;ethyl ether, ethylene glycol d;methyl ether, tetrahydrofuran, d;oxane, th;oan;sole and ~,~'-d;-chlorod;ethyl ether; n;trohydrocarbons, such as nitro-methane, n;troethane, n;trobenzene, o-, m- and p-chloro-nitrobenzene and o-nitrotoluene; n;triles, such as aceto-n;trile, butyron;trile, isobutyronitrile, benzonitrile and m-chlorobenzonitrile; aliphatic and cycloaliphatic hydro-carbons, eg. heptane, pinane, nonane, o-, m- and p-cymene, gasol;ne fract;ons bo;l;ng w;th;n a range from 70 to 190C, cyclohexane, methylcyclohexane, decal;n, petro-leum ether, hexane, naphtha, 2,2,4-tr;methylpentane, Z,2,3-tr;methylpentane, 2,3,3-tr;methylpentane and octane;
esters, eg. ethyl acetate, ethyl acetoacetate and ;so-butyl acetate; am;des, eg. formam;de, methylformam;de andd;methylformam;de, and ketones, eg. acetone and methyl ethyl ketone, as well as m;xtures of these. Advantageously, the solvent ;s used ;n an amount of from 1D0 to 2,000, preferably from 200 to 700, X by weight, based on the start;ng materi~als.
Any convent;onal ac;d acceptor can be used for process b). Such ac;d acceptors preferably ;nclude ter-t;ary am;nes, alkaline earth metal compounds, ammon;um compounds and alkal; metal compounds, as well as m;xtures of these. However, z;nc compounds can also be used. Ex-amples of su;table bas;c compounds are potass;um hydrox-;de, sod;um hydrox;de, potassium carbonate, sodium - - ~z4~680 ~ ~ ~ O.Z. 0050/36555 carbonate, l;thium hydroxide, Lithium carbonate, sod;um bicarbonate, potassium bicarbonate, calcium hydroxide, calcium oxide, bar;um oxide, magnesium hydroxide, magne-sium oxide, barium hydroxide, calcium carbonate, magnesium carbonate, magnesium bicarbonate, magnes;um acetate, zinc hydroxide, zinc oxide, zinc carbonate, zinc bicarbonate, zinc acetate, sodium formate, sodium acetate, trimethyl-am;ne, triethylamine, tripropylam;ne, tr;isopropylamine, tr;butylamine, triisobutylamine, tri-sec.-butylamine, tri-tert.-butylamine, tribenzylam;ne, tricyclohexylamine, tri-amylamine, di;sopropylethylam;ne, tr;hexylamine, N,N-d;me-thylanil;ne, N,N-d;ethylan;l;ne, N,N-dipropylaniline, N,N-dimethyltoluid;ne, N,N-d;ethy~to~u;dine, ~ dipropyl-toluidine, N,N-dimethyl-p-am;nopyr;d;ne, N,N-d;ethyl-p-aminopyr;d;ne, N,N-dipropyl-p-aminopyridine, N-methyl-pyrrolidon~, N-ethyl-pyrrolidone, N-methylpiperidine, N-ethylpiperidine, N-methylpyrrol;dine, N-ethylpyrrol;dine, N-methylimidazole, N-ethylimidazole, N-methylpyrrole, N-ethylpyrrole, N-methylmorpholine, N-ethylmorpholine, N-methylhexamethylene;mine, N-ethylhexamethyleneim;ne, pyridine, quinoline, -picoline, -picoline, isoquinoline, pyrimidine, acridine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethyl-ethylenediamine, quinoxaline, quin-azoline, N-propyldiisopropylamine~ N,N'-dimethylcyclo-hexylamine, 2,6-lutidine, 2,4-lutidine, trifurylamine and triethylenediamine.
The starting compounds are prepared by a conven-ional method. For example, the phenylhydrazines of the formula V are obtained from the correspondins anilines by diazotization and reduction, by a conventional method (Houben-Weyl, Methoden der organischen Chemie, volume 10/2, page 180, Georg Thieme Verlag, Stuttgart, 1967). The con-version to the corresponding pyrazone can be carried out without isolating the hydrazines, but purer products are obtained if the phenylhydrazines are isolated as hydro-chlorides beforehand.

124~6~30 - 9 - O.Z. ~050/36555 Some of the anilines are also known from the lite-rature tGerman La;d-Open Application DOS 2,846,723).
Those which are not known can be prepared by a conventional method.
The oxidat;on of th;oethers to the corresponding sulfoxides or sulfones ;s a well known react;on and can be carried out in a conventional manner.
The Examples wh;ch follow ;llustrate the prepara-t;on of the compo-unds of the formula I. Parts by we;ght bear the same relat;on to parts by volume as that of the k;logram to the liter.

a) A suspens;on of 49.8 parts by weight of 3-phenoxy-methylani~ine in 400 parts by voLume of gLaciaL acet;c ac;d and 70 parts by volume of concentrated hydrochlor;c ac;d was reacted w;th a solut;on of 17.25 parts by weight ~ of sodium nitrite in 45 parts by volume of water at from 10 to 20C. A solution of 118 parts by weight of SnCl2.2H2û`;n 8û parts by volume of concentrated hydro-chlor;c ac;d was then added, the m;xture was cooled to 0C
and the correspond;ng hydraz;ne hydrochloride was isolated by filter;ng ;t off under suct;on.
b) A suspens;on of 43.2 parts by we;ght of the hydra-z;ne hydrochlor;de ;solated ;n th;s manner and 33.4 parts by we;ght of mucochlor;c ac;d in 200 parts by volume of acet;c acid was heated at the bo;l for 10 m;nutes, after which the react;on mixture was cooled, and st;rred into 1,000 parts by volume of water. The precipitate was then f;ltered off under suct;on and recrystallized from ethanol.
53 parts by weight of 1-t3'-phenoxymethylphenyl)-4,5-di-chloropyr;daz-6-one of melt;ng po;nt 92 - 94C were obtained.
c) A suspens;on of 15 parts by weight of this product, 2.3 parts by weight of sodium methylate and 0.1 part by weight of N-methylpyrrolidone ;n 15û parts by volume of absolute toluene was stirred at 60C for 2 hours. The resulting solution was diluted with 20û parts by volume of lZ4Q680 - 10 - O.Z. 0050/36555 ether, treated with twice 100 parts by volume of water, dr;ed and f;ltered, and the f;ltrate was evaporated down under reduced pressure. The oily residue was triturated w;th d;isopropyl ether, and the pr~duct was filtered off under suction. 13 parts by weight ~9ûX of theory) of 1-(3'-phenoxymethylphenyl~-4,5-dimethoxypyridaz-6-one of meLt;ng point 82 - 85C were obtained (compound No. 1).
The compounds Gf the formula I which are l;sted in Table 1 below can be prepared by the method described in the Example above:

- ~Z4~680 - 11 - O.Z. 0050/36555 m o EC
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N
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N N N N N N N T N IN IN TN IN I I I I I I I , I
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N I I I I I I I T T I IN IN TN IN TN IN N N N N N N N
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- 14 - 0 . Z . 0050/36555 E
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124~36~30 - 19 - O.Z. 0050/36555 The 4,5-dimethoxypyridazones of the formula I may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emul-05 sions, oil dispersions, pastes, dusts, broadcastingagents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil frac-tions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydro-carbons such as benzene, toluene, xylene, paraffin, tetra-hydronaphthalene, alkylated naphthalenes and their deriva-tives such as methanol, ethanol, propanol, butanol, chloro-form, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar sol-vents such as dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone, and water are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dis-persions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsify-ing or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalene-sulfonic acid, lauryl ether sulfate, fatty alcohol sul-lZ~U680 - 2~ - O.Z. 0050/36555 fates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, hepta-decanols, and octadecanols, salts of sulfated fatty alco-hol glycol ethers, condensation products of sulfonated 05 naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesul-fonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, eth-oxylated octylphenol and ethoxylated nonylphenol, alkyl-phenol polyglycol ethers, tributylphenyl polyglycolethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oi l, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingre-dients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and prefer-ably 0.5 to 90, ~j by weight of active ingredient.
Examples of formulations are given below.

I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A
mixture is obtained which is suitable for application in the form of very fine drops.

lZ~4.,'6.80 - 21 ~ O.Z. 0050/36555 II. 20 parts by weight of compound no. 3 is dissol-ved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-OS amide, 2 parts by weight of the calcium salt of dodecyl-benzenesulfonic acid, and 2 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
III. 20 parts by weight of compound no. 5 is dissol-ved in a mixture consisting of 60 parts by weight of ln cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 mol es of ethylene oxide and 1 mole of isooctylphenol, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil.
IV. 20 parts by weight of compound no. 33 is dissol-ved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02~; by weight of the active ingredient.
V. 80 parts by weight of compound no. 126 is well mixed with 3 parts by weight of the sodium salt of diiso-butylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill.
VI. 5 parts by weight of compound no. 130 is intimately mixed with 95 parts by weight of particulate kaolin. A dust is obtained containing 5% by weight of the active ingredient.
VII. 30 parts by weight of compound no. 108 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface OL

~z~6~30 - 22 - O.Z. 0050/36555 this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 20 parts of compound no. 28 is intimately mixed with 2 parts of the calcium salt of dodecylbenzene-05 sulfonic acid, 8 parts of a fatty alcohol polyglycolether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
The active ingredients, or agents containing them, may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well when they are applied postemergence, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensiiive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).
The amount of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.05 to 3 kg/ha and more, but is preferably from 0.1 to 1.0 kg/ha.
The herbicidal action of 4,5-dimethoxypyridazones of the formula I is demonstrated in greenhouse experiments.
The vessels employed were plastic flowerpots having a volume of 300 cm3, and which were filled with a sandy loam containing about 1.5~; humus. The seeds of the test plants were sown shallow, and separately, according to species.
For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per hectare. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken 12~lt680 - 2~ - O.Z. 0050/36555 root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingre-dients.
For the postemergence treatment, the plants were 05 first grown in the vessels to a height of from 3 to 15 cm, depending on growth form, before being treated. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had been grown from seedlings and were transplanted to the pots a few days before treatment. No covers were placed on the pots in this treatment method. The application rates for postemergence treatment were 0.25 and 0.5 kg of active ingredient per hectare.
The pots were set up in the greenhouse - species from warmer areas at from 20 to 35C, and species from moder-ate climates at 10 to 25C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was O to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.
The plants used in the experiments were Abutilon theophrasti, Amaranthus retroflexus, Arachis hypogaea, Cassia tora, Centaurea cyanus, Chenopodium album, Datura stramonium, Desmodium tortuosum, Euphorbia geniculata, Galium aparine, Helianthus annuus, Ipomoea spp., Lamium spp., Mercurialis annua, Polygonum persicaria, Sinapis alba and Triticum aestivum.
In investigations into herbicidal properties, for example compounds nos. 1, 3, 28, 33, 108 and 126 had a very good action on Sinapis alba when applied preemergence at a rate of 3.0 kg/ha.
On postemergence application, for instance compounds 35 nos. 5, 129, 130 and 137, applied for example at a rate of 0.25 kg/ha, had a considerable herbicidal action on a number of unwanted broadleaved plants. Compounds nos. 33 I

12~ 6~
- 24 - O.Z. 0050/36555 and 3 selectively combatted unwanted plants at rates of 0.25 and 0.5 kg/ha, crops such as groundnuts and wheat being only slightly damaged, if at all. Unwanted broad-~
leaved plants in sunflowers where selectively combatted by 05 compounds 3, 14, 33 and 126 at rates of 0.125 and 0.25 kg/ha.
In view of the many application methods possible, the 4,5-dimethoxypyridazones of the formula I may be used in a large number of crop plants for removing unwanted plant growth, especially broadleaved annual species. The following crops may be mentioned by way of example:
sotanical name Common name Allium cepa onions 15 Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets 20 Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets Brassica napus var. napus rapeseed Brassica napus var. napobrassica swedes Brassica napus var. rapa turnips Brassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons 30 Citrus maxima grapefruits Citrus reticulata mandarins Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants 35 Cucumis melo melons Cucumis sativus cucumbers Cynodon dactylon Bermudagrass in turf and lawns ~z4~80 - 25 - O.Z. 0050/36555 Botanical name Common name Daucus carota carrots Elais guineensis oil palms 05 Fragaria vesca strawberries Glycine max soybeans Gossypium hirsutum (Gossypium arboreum cotton Gossypium herbaceum Gossypium vitifolium) Helianthus annuus sunflowers Helianthus tuberosus Hevea brasiliensis rubber plants Hordeum vulgare barley 15 Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils 20 Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) 25 Mentha piperita peppermint Musa spp. banana plants Nicothiana tabacum tobacco (N. rustica) Olea europaea olive trees 30 Oryza sativa rice Panicum miliaceum Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucum Petroselinum crispum parsley spp. tuberosum - 124~680 - 26 - O.Z. 0050/36555 Botanical name Common name _ Picea abies Norway spruce Abies alba fir trees 05 Pinus spp. pine trees Pisum sativum English peas Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees 10 Prunus persica peach trees Pyrus co~rununis pear trees Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Ricinus communis castor-oil plants 15 Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Sorghum dochna Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aesti~um wheat 25 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes `30 Zea mays Indian corn, sweet corn, maize To increase the spectrum of action and to achieve synergistic effects, the 4,5-dimethoxypyridazones of the formula I, or agents containing them, may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups.

- 27 ~ 6~0 o.z. 0050i36555 Examples of suitable mixture components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, 05 triazinones, uracils, benzofuran derivatives, cyclohexane--1,3-dione derivatives, etc., and others.
It may also be useful to apply the novel compounds, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria.
The compounds may also be mixed with sol utions of mineral salts used to remedy nutritional or trace element deficien-cies. Non-phytotoxic oils and oil concentrates may also be added.

Claims (13)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A substituted 4,5-dimethoxypyridazone of the formula (I), where X and Y independently of one another are each oxygen, sulfur, a sulfinyl group or a sulfo group, R1 and R2 inde-pendently of one another are each hydrogen or C1-C4-alkyl, Z , Z and Z independently of one another are each hydrogen, halogen, nitro, cyano, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylmercapto, C1-C4-halo-alkylmercapto, C1-C4-alkylsulfinyl or C1-C4-alkylsulfonyl, n and p are each O or 1 and m and q are each O to 8 with the proviso that m and q are not simultaneously equal to 0.

2. A substituted 4,5-dimethoxypyridazone of the formula I as claimed in claim 1, where X and Y independently of one another are each oxygen or sulfur, R1 and R2 inde-pendently of one another are each hydrogen or C1-C4-alkyl, Z1, Z2 and Z3 independently of one another are each hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy, n and p are each 0 or 1 and m and q are each 0 to 8 with the proviso that m and q are not simultaneously equal to 0.

3. A substituted 4,5-dimethoxypyridazone of the formula I as claimed in claim 1, where R1 and R2 are hydro-gen, Z1 is hydrogen, Z2 and Z3 are halogen, n is 0 m is 1, p is 1, and q is 0.

4. A substituted 4,5-dimethoxypyridazone of the formula I as claimed in claim 1, where R1 and R2 are hydro-gen, Y is oxygen, Z1 and Z2 are hydrogen, Z3 is fluorine in the 3-position, n is 0, m is 1, p is 1, and q is 0.

5. A substituted 4,5-dimethoxypyridazone of the formula (I) as claimed in claim 1, where R1 and R2 are hydrogen, Y is oxygen, Z1 and Z2 are hydrogen, Z3 is trifluoromethyl in the 3-position, n is O, m is 1, p is 1, and q is 0.

6. A process for the manufacture of substituted 4,5-dimethoxypyridazones of the formula (I) as defined in claim 1, wherein a dihalopyridazone of the formula (IV):

(IV), where X, Y, R1, R2, Z1, Z2, Z3, n, m, p and q have the meanings given in claim 1 and Hal is halogen, is reacted with about the stoichiometric amount of an alkali metal methylate in the presence of an inert organic solvent at no higher than 100° C.

7. A process for the manufacture of substituted 4,5-dimethoxypyridazones as defined in claim 6, wherein a dihalopyridazone of the formula (IV) is used which is manufactured by reaction of a phenylhydrazine of the formula (V):

(V) where X, Y, R1, R2, Z1, Z2, Z3, n, m, p and q have the meanings given in claim 1, with a 3-formyl-2,3-dihaloacrylic acid of the formula (VI):

(VI) where Hal is chlorine or bromine, initially at room temperature in the presence of a solvent, and subjection of the resulting dihaloacrylic acid semicarbazone to a cyclization reaction.

8. A process for the manufacture of substituted 4,5-dimethoxypyridazones of the formula (I) as defined in claim 1, wherein a 4,5-dimethoxypyridazone of the formula (II):

where X is oxygen or sulfur, is reacted with about the stoichiometric amount of an alkyl halide of the formula (III):

(III) where R1, R2, Y, Z1, Z2, Z3, m, p and q have the meaning given in claim 1 and Hal is halogen, bromine, in the presence of an inert organic solvent and in the presence or absence of an acid acceptor, at from 0 to 150° C.

9. A herbicide containing at least one inert additive and an effective amount of a 4,5-dimethoxypyridazone of the formula (I) as defined in claim 1 or 2.

10. A herbicide containing at least one additive and an effective amount of a 4,5-dimethoxypyridazone of the formula (I) as defined in claim 3, 4 or 5.

11. A process for combatting the growth of unwanted plants, where in from 0.05 to 3 kg of a 4,5-dimethoxypyridazone of the formula (I) as defined in claim 1 or 2 is applied per hectare.

12. A process for combatting the growth of unwanted plants, where in from 0.05 to 3 kg of a 4,5-dimethoxypyridazone of the formula (I) as defined in claim 3, 4 or 5 is applied per hectare.

13. A process for the manufacture of substituted 4,5-dimethoxypyridazones of the formula (I) as defined in claim 1, wherein:
either a dihalopyridazone of the formula (IV):

(IV) where X, Y, R1, R2, Z1, Z2, Z3, n, m, p and q have the meanings given in claim 1 and Hal is halogen, is reacted with a substantially stoichiometric amount of an alkali metal methylate in the presence of an inert organic solvent at a temperature not higher than 100° C, or a 4,5-dimethoxypyridazone of the formula (II):

(II) where X is oxygen or sulfur, is reacted with a substantially stoichiometric amount of an alkyl halide of the formula (III):

(III) where R1, R2, Y, Z1, Z2, Z3, m, p and q have the same meanings as in claim 1 and Hal is halogen, in the presence of an inert organic solvent at a temperature of from 0 to 150° C.